New alkoxy derivatives of anthanthrone and process of making same



No Drawing. Application patented May 19, 1931 RICHARD HERZ, or 'FRAIIKFoRT-oN-TIIE-MAIN, AND WERNER zERWEcK, or; FECHEN- HEIM, NEAR FB-ANKFOET-ON-THE-MAIN, :GERMANY, ASSIGNORS -'.ro GENERAL p TESIPATEQNTIQCFFICEY 'ANILINE woRKs, me, on NEW YORK, N. Y., A CORPORATION on DELAWARE NEW ALKOXY DERIVATIVES or" ANTIIAN'I' IRONE AND In U. S. patent of Richard Herz and Fritz "'"Schulte N;'1,72s,995 of Sept. 24,1929, al-

koxyderivatives I of naphtho'styril are described. I p I 'We have found a'process for manufacturing new alkox'yderivatives of anthant-hrone by starting from these alkoxynaphtho'styril compounds. Our process consists in saponifying the alkoxynaphthostyrils 'to the correspondingalkoxyderivatives of 1-aminonaph thalenegS-carboxylic acid diazotizing these derivatives, treating diazocompoun'ds thus obtained with reducing agents and-subjecting finally the alkoxyderiv'atives of; 1.1"-din aphthyl-8.8-dicarboxylio acid thus obtained to the action of acid condensing agents. The cost of the reaction may be illustrated by the following scheme of formulas:

, dilute cau tic O-alkyl )sslkali solutions alkoxyderivatives ofI-aminonaphthaacid condensalkyl ing agents I alkoxyderivat ives of 1.1-dina'phthy1-8.8- I

dicarboxylic acid The alkoxyderivatives of .lQlT-dihaPhthyl- 8 d rbQXy i id, btained he la dialkoxyderivatlves of r ooEss on MAKII G SAME filedO' ctober 7, 1927; serial No 224,75s, andin Germany October' 13,"1926,

intermediates of our combined process, are also new compounds; p w p The new alkoxyderivatives of anthanthrone obtained in a pure state with an excellent yield according to our invention correspond probably to the aforesaid general formula, they are when dry reddish to brownish colored powders, soluble in ooncentrated sulfuric acid with, a reddish to greenish color. They form with an'alkaline hydrosulfit'e solution violet colored vats anddye cotton therefrom 'violettints, turningto orange to reddish shadesofian excellent fast ness, when exposed tothe-air or soaped;

1 In order to further illustrate our inven tion the following examples are given the parts being by weight and all temperatures anthanthrone ena ed w:

We wish it however the particular conditions nor to the specific products mentioned therein.

Example 200 parts of 5-1nethoxyna-phthostyril of the formula:

con. (see Example 6?) of the aforesaid U. S. Patent No. 1,728,995) are by boiling for instance with a caustic soda solution of 10% saponifled to the'sodi'um' salt of the 5-methoxy-l- 217 parts of this acid'are diazotized and the diazocompound is introduced at an ordinary temperature in anammoniacal solution of cuprous oxide, prepared fro1n500 partsof sulfate of copper by means of sulfur dioxide. The formed 5.5.-dim ethoXy-1.1d'inaphthyl-8.8-dicarboxylic acid of the for mula:

5 4 Y CH3 is isolated by acidifying the reaction mass.

It is an almost colorless powder, soluble in dilute solutions of caustic alkalie's. and of alkali carbonates. i

This step of our combined process is covered by U. S. Patent No. 1,684,272 of Herz and Zerweck, issued Sept. 11, 192.8. I

1 part of this 5.5-dimethoXy-1.1-dinaphthyl-8.8-dicarboxylic acid is introduced v while cooling into 25 parts of concentrated sulfuric acid of 66 B. The solution turns at first to orange red, then to intense green With a brilliantrcd fluorescence. After stirring for some hours the mass is poured on Water, the dyestuif separating in red flakes is filtered, washed with water and dried. he formed dimethoxy-anthanthrone corresponding probably to the formula:

is when dry a brilliant red powder, soluble in concentrated sulfurlc acld wlth an emerald green color and a strong red fluorescence.

Recrystallized from boiling trichlorobenzene,

it is obtained as red needles. From a violet hydrosulfite' vat cottonis dyed violet shades turning, when exposed to the air or soaped,

to a brilliant reddish orange of a good fastness.

hen starting from 5-ethoxynaphthostyril in, the same manner'the corresponding diethoxyanthanthrone is obtained, which is a dyestuif of very similar properties.

When starting from the isomeric 6-a1koXynaphthostyrils, for instance from G-methoxynaphthostyril (of. example 4 of the aforesaid U. S. Patent No. 1,728,995) according to our combined process an isomeric dimethoxyanthanthrone is obtained, crystallizing'from trichlorobenzene as brownish little rods, soluble in concentrated sulfuric acid with a claret-red color, forming with an alkaline. hydrosulfite solution a violet vat and dyeing cotton therefrom yellowish orange shades.

In the-same manner the process may be. car- -ri-edout by using the isomeric 3-alkoxynaphthastyrils as parent materials.

We claim:

. 1. A process for producing new alkoXy-' derivatives of anthanthrone which process -comprises saponifying alkoXyderi-vatives of naphthostyrils of the general formula:

oo- .NH

to the corresponding alkoxyderivatives of 1- aminonaphthalene-S-carboxylic acid, diazotizing them, treating the diazocompounds thus obtained with reducing agents and subjecting finally the alkoxyderivativcs of 1.1- dinaphthyle8.8edicarboxylic acid thus ob.- tained tothe action of acid condensing agents.

2. As new compounds alkoxyderivatives of of the formula:

' rsossis anthanthrone corresponding probably to the general formula: v 7

which compounds are when dry reddish colored powders, soluble in concentrated sulfuric acid with a reddish to greenish color, forming with an alkaline hydrosulfite solution violet colored vats and dyeing cotton therefrom orange to reddish shades of an excellent fastness, which compounds are substantially identicalwith products obtainable by saponifying alkoxyderivatives of naphthostyrils of the general formula:

to the corresponding alkoxyderivatives of 1-aminonaphthalene-8 carboxylic acid, diazotizing them, treating the diazocompounds thusobtained with reducing agents and subjecting finally the alkoxyderivatives of 1.1-

dinaphthyl-S.Sfldicarboxylic acid thus ob tained to the action of acid condensing agents.

3. A process for producing new alkoxyde rivatives of anthanthronewhich process comprises saponifying 5-alkoxynaphthostyrils OC-NH a 0 8mg 7 to the corresponding 5-alkoxy-1-aminonaphthalene-S-carboxyliG acids, diazotizing them,

treating the diazocompounds thusobtained with reducing agents and subjecting finally the 5.5-dialkoxy-l.1 dinaphthyl8.8-dicarboxylic acids thus obtainedto the action of I said condensing agents. 7 I

4:. As new compoundsalkoxyderivatives of anthanthrone, corresponding probably to the formula: 1

Alkyl- O formula:

7 let shades, turning to a brilliant reddish orange of a good fastness, whe'n exposed to the air or soaped, which compounds are substantially identical with products obtainable by saponifying 5-alkoxynaphthostyrils of the i T" i i i V I A i I alkyl "so; a

to the corresponding 5-alkoxy larninonaph thalene-8 carboxy1ic acids, I diazotizing them, treating the diazocompounds thus obtained with reducing agents and subjecting finally 5.5 -dialkoxy 1 1 i dianaphthyl 8. 8=- dicar- ,boxylic acids thus obtained to the action of acid condensing agents; I

5. As new compounds, alkoxy derivatives of anthanthrone corresponding probably to the formula: i

' which compounds are, when dry, reddish col- 7 ored powders, soluble in concentrated sulfuric acid with a reddish to greenish color,

forming with an alkaline hydrosulfite solution violet colored vats, and dyeing cotton therefrom yellowish-orange to reddish shades of good fastness.

6. As a new compound, dimethoxyanthanthrone of the following formula:

which compound crystallizes from trichloroben'zene as brownish little rods, is soluble in concentrated sulfuric acid with a claretred color and forms with an alkaline hydrosulfite solution a violet vat from which cotton is dyed yellowish-orange shades of a good fastness. 7

7. As a new compound, dimethoxyanthanthrone of the following formula:

which compound is, when dry, a brilliant red powder, soluble inoonoentrated sulfuric acid with an emerald green color and a strong red fluorescence, forming with an alkaline hydrosulfite solution a violet vat from which cotton is dyed violet shades which turn to brilliant reddislrorange shades of good fastness, when exposed to the air or soaped.

In testimony whereof, we affix our signatures.

RICHARD HERZ. WVERNER ZERWECK.

CERTIFICATE OF CORRECTION.

Patent No. 1,805,913. Granted May 19, 1931, to

RICHARD HERZ ET AL.

It is hereb certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 3, line 53, claim 3, for the word "said" read acid; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 14th day of July, A. D. 1931.

M. J. Moore, (Seal) Acting Commissioner of Patents 

